JP2014531501A - Multilayer pressure sensitive adhesive film having a pressure sensitive adhesive comprising a (meth) acrylate ester of 2-alkylalkanol - Google Patents

Abstract

The present invention is a multi-layer pressure sensitive adhesive (PSA) comprising a first pressure sensitive adhesive layer and at least one opposing layer, wherein the first pressure sensitive adhesive layer comprises a) A (meth) acrylate ester of 2-alkylalkanol, wherein the 2-alkylalkanol has a molar average carbon number of 12 to 32, and optionally b) (meth) acrylate (meth) acrylate A) and b) a (co) polymer of (meth) acrylate ester with an average alkanol molar carbon number of 12 to 32 of a) and b) (meth) acrylic acid ester. Wherein the at least one opposing layer comprises at least one filler material selected from the group of filler particles, the filler particles comprising: Is a foam perlite, it relates to a multilayer pressure-sensitive adhesive (PSA). The invention also relates to the production of such multilayer PSA films and methods for their use. [Selection figure] None

Description

  The present invention relates to a multilayer pressure sensitive adhesive (PSA) film having a first pressure sensitive adhesive layer and at least one opposing layer. The present invention also provides a method for producing such a multilayer PSA film.

  Pressure sensitive tape exists virtually everywhere in the home and the workplace. In its simplest configuration, the pressure sensitive tape comprises an adhesive and a backing, and the overall structure is tacky at the temperature of use and can be applied to various substrates with only moderate pressure to form a bond. Glue. In this manner, the pressure sensitive tape constitutes a complete and self-contained fastening system.

  According to the Pressure Sensitive Tape Council, pressure sensitive adhesives (PSAs) are known to have the following properties: That is, (1) strong and permanent adhesiveness, (2) adhesiveness below finger pressure, (3) sufficient holding power to the adherend, and (4) sufficient to be peeled cleanly from the adherend Cohesive strength. Materials that have been found to function well as PSA include polymers that are designed and formulated to exhibit the required viscoelastic properties and provide the desired balance of tack, peel adhesion, and shear retention. . PSA is usually characterized by being tacky at room temperature (eg, 20 ° C.). PSA does not embrace the composition only by stickiness or adhesion to the surface.

These requirements generally are, Pocius in Adhesion and Adhesives Technology: An Introduction, 2 nd Ed. , Hanser Gardner Publication, Cincinnati, OH, 2002, evaluated by test means designed to measure adhesion, adhesion (peel strength), and adhesion (shear retention), respectively. These measurements work together and constitute a balance of properties often used in characterizing PSA.

  With the increasing use of pressure sensitive tape over the years, the level of performance required is higher. For example, the shear holding force originally intended for supporting moderate loads at room temperature has now increased significantly to accommodate a variety of applications from the standpoint of operating temperature and load. The so-called high performance pressure sensitive tape is a tape capable of supporting a load at a high temperature for 10,000 minutes. Enhanced shear retention is usually achieved by cross-linking PSA, but considerable care must be taken to maintain a high degree of adhesion and adhesion in order to maintain the aforementioned balance of properties. There is.

  A variety of pressure sensitive adhesive (PSA) materials are now available, such as raw natural or synthetic rubber, block copolymers, and acrylic ester-based polymer compositions. Due to the increased performance requirements for PSA, there has been a great focus on the development of acrylate PSA, especially over the last half century. By strictly adjusting the acrylic PSA, it can provide a number of desired properties, such as elasticity, tackiness, transparency, oxidation resistance and sunlight resistance, and in addition, is required for tape application. It can have the necessary adhesion and sticking degree.

The core of all PSAs is a desirable balance of adhesion and stickiness. In many cases, this balance is achieved by optimizing physical properties such as glass transition temperature and elastic modulus of the acrylic acid elastomer. For example, the glass transition temperature (T _g ) or elastic modulus of the elastomer is too high, and the Durquist standard for tackiness (at room temperature and a vibration frequency of 1 Hz, 30 N / cm ² (3 × 10 ⁶ dynes / cm ² ) (Storage modulus of (300 kPa)), the material is not tacky and is not useful as a PSA material. In such cases, often, the use of high resin polymer having T _g in the low molecular weight low T _g in (tackifiers) or low molecular weight polymer (plasticizer), T _g and modulus PSA Is adjusted to the optimum range.

Current acrylic ester PSA is typically primarily composed elastomeric polymer from the non-polar monomer having low T _g, and a small amount of a polar acrylic monomer (e.g., acrylic acid). Widely used in PSA, 2 kinds of acrylate low The _{T g,} 2-ethylhexyl an acrylate (EHA) and isooctyl acrylate (IOA), provides the alkyl chain of the respective number 8 carbon atoms _{(C 8)} To do. As alkyl chains become longer or shorter, they have various disadvantages in terms of PSA performance. For example, shorter alkyl chains (eg, butyl acrylate-C ₄ ) significantly increase both the T _g and elastic modulus of the elastomer, with room temperature storage modulus of 30 N / cm ² (3 × 10 ⁶ dynes / cm ^2). ) (300 kPa) will increase. Alternatively, longer alkyl chains (eg, lauryl acrylate-C ₁₂ ) may induce crystalline groups within the polymer, which will significantly reduce the degree of tack as well.

  From U.S. Pat. No. 4,818,610 (Zimmerman et al.) A pressure sensitive adhesive tape comprising a plurality of superposed layers, at least one outer layer being a pressure sensitive adhesive layer, is known. The pressure sensitive adhesive layer may be obtained from a polymerizable mixture containing an acrylate.

  There remains a need for multilayer PSA films with improved adhesive properties, particularly with respect to peel force and shear resistance, without competing with the technical advantages associated with pressure sensitive adhesive films known in the art.

  Pressure sensitive materials known from the prior art are sufficient on so-called LSE substrates, ie substrates having a low surface energy such as polyolefin surfaces or clearcoat surfaces, in particular clearcoats for vehicles such as cars. Often does not provide a good adhesion. In particular, the peel force resistance on these difficult-to-fix substrates often does not meet the requirements, especially under changing environmental stresses such as temperature and humidity. This disadvantage may be partially overcome by the addition of higher amounts of tackifier. However, excessive use of tackifiers often results in the disadvantage of reduced shear resistance due to the plasticizing effect of the tackifier. Also, the tackifier may move into the substrate to which the adhesive tape is affixed, which may lead to unwanted color changes or reduced stability.

  Another problem with tackified pressure sensitive adhesives containing conventional (meth) acrylic elastomeric materials is that these formulations appear cloudy and loss in the characteristic transparency of conventional (meth) acrylic elastomeric materials This means that This haze is an indication of limited or incomplete compatibility of the tackifier and elastomeric material. Reduced compatibility can lead to degradation of adhesive properties, as evidenced by loss of tack over time or reduced peel adhesion.

  Accordingly, an object of the present invention is to provide a multilayer PSA of the type described above that combines good peel force and high shear resistance on LSE (low surface energy) substrates without requiring the use of excessive tackifiers. Is to provide a film. This object is solved by a multilayer pressure sensitive adhesive (PSA) film according to the invention.

According to one aspect, the present invention is a multilayer pressure sensitive adhesive (PSA) film having a first pressure sensitive adhesive layer and at least one opposing layer, wherein the first pressure sensitive adhesive layer comprises:
a) a (meth) acrylate ester of a 2-alkylalkanol, wherein the 2-alkylalkanol has an average molar carbon number of 12 to 32, and optionally,
(b) a (meth) acrylate ester of C _1-12 alkanol, wherein (a) and b) (meth) acrylate ester having an average alkanol molar carbon number of 12-32;
Wherein the at least one opposing layer comprises at least one filler material selected from the group of filler particles, wherein the filler particles are expanded perlite. The average number of moles of 2-alkylalkanol is the sum of the number of moles of each alkanol (2-alkylalkanol and C _1-12 alkanol) multiplied by the number of carbons of each alkanol, and the result is defined by the following formula: It relates to a multilayer pressure sensitive adhesive film, calculated by dividing by the total number of moles of alkanol as is.

  Indeed, it has been found that multilayer PSA films combine high peel force and high shear force resistance on LSE substrates as described above.

  The multilayer PSA films of the present invention are therefore particularly suitable for bonding to low energy surfaces such as polyolefin surfaces and clearcoat surfaces. The multilayer PSA film of the present invention is particularly suitable for bonding on the clearcoat surface of vehicles such as cars.

  In another aspect, the present invention is a method for producing a multilayer pressure sensitive adhesive film as described above, wherein the first pressure sensitive adhesive layer and the opposing layer are superimposed on each other. About.

  In yet another aspect, the present invention provides a PSA film for bonding a first pressure sensitive adhesive layer of a multilayer pressure sensitive adhesive film as described above to an LSE substrate surface, preferably a clearcoat surface. About the use of.

According to the present invention, the pressure sensitive adhesive for use in the multilayer PSA film is a (meth) acrylate adhesive comprising at least one monomer derived from a 2-alkyl alkanol, ie Guerbet alkanol. The pressure sensitive adhesive may further comprise at least one (meth) acrylic acid ester of C _{1 to} C ₁₂ alkanol, at least one acid functional monomer, and optionally one non acid functional polar monomer. The above may be included. The pressure sensitive adhesive of the present invention may optionally contain other monomers that may be added to improve the physical properties of the adhesive, such as crosslinkers, and other additives such as tackifiers or plasticizers. including.

  The pressure sensitive adhesive composition for use in the multilayer PSA film of the present invention may be used only for the first pressure sensitive adhesive layer, or may be further modified such as an opposing layer and / or an intermediate layer. May also be used for the resulting layer.

The average carbon number of 2-alkylalkanol of Guerbet (meth) acrylate is 12 to 32 (C _{12 to} C ₃₂ ), preferably 12 to 20 (C _{12 to} C ₂₀ ). When any b) C _1-12 alkanol (meth) acrylate is present, the carbon number molar average of a) and b) (meth) acrylic acid ester alkanol is 12-32 (C ₁₂ -C ₃₂ ), preferably is _{12~20 (C 12 ~C 20).} Mole carbon number average is calculated by totaling the number of moles of each alkanol (Guerbet and C _1-12 alkanol), multiplying by the number of carbons of each alkanol, and dividing the resulting value by the total number of moles of alkanol. Can:

The (meth) acrylic acid ester monomer of the 2-alkyl alkanol is derived from a C ₁₂ -C ₃₂ Guerbet alkanol, preferably a C ₁₂ -C ₂₀ Guerbet alkanol. These Guerbet alkanols are obtained by base-catalyzed self-condensation of linear and / or branched alkanols containing 4 to 14 and preferably 6 to 12 carbon atoms. For the preparation of Guerbet alkanols, primary or secondary alkanols can be used.

It is known in the art that Guerbet alkanols can be generated from the same or different alkanols (ie, homo or hetero systems). That is, a Guerbet alkanol is a condensation product of two alkanol molecules linked at the beta carbon of an alkanol that possesses hydroxyl functionality; that is, a 2-alkylalkanol. The resulting product is therefore a branched primary alkanol containing one hydroxyl group. A mixture of starting materials can be used in the Guerbet reaction and condensed to a mixture of alkanol products. Guerbet alkanol products derived from short chain alkanols can also be obtained. From the standpoint of polarity, _Tg, and elastic modulus, it is desirable to use a Guerbet alkanol having a molar carbon number average of 12 to 32. An overview of Guerbet alkanols is given in A. J. et al. O'Lennick in Soap Cosm. Chem. Spec. (April) 52 (1987). Reference may also be made to US Pat. No. 6,419,797 (Sherf et al.) For a method for producing Guerbet alkanols.

  (Meth) acrylate ester monomers derived from Guerbet alkanols have the following formula I:

のものであり、式中、Ｒ^{Ｇｕｅｒｂｅｔ}は、Ｃ_１２〜Ｃ_３２ ２−アルキルアルカノールから誘導され、即ち、アルキル基は、２箇所で分岐し、Ｒ^３は、Ｈ又はＣＨ_３である。

^Where R ^Guerbet is derived from a C ₁₂ -C ₃₂ 2- ^alkylalkanol , ie, the alkyl group is branched at two positions and R ³ is H or CH ₃ .

  Preferably, the (meth) acrylate ester monomer derived from Guerbet alkanol has the formula II:

のものであり、式中、Ｒ^１及びＲ^２は、それぞれ独立して、Ｃ_４〜Ｃ_１４飽和で、かつ分枝又は直鎖のアルキルであり、Ｒ^３はＨ又はＣＨ_３である。

Where R ¹ and R ² are each independently C ₄ -C ₁₄ saturated and branched or straight chain alkyl, and R ³ is H or CH ₃ .

  The pressure sensitive adhesive composition for use in the multilayer PSA film of the present invention may comprise a Guerbet (meth) acrylate homopolymer. In many preferred embodiments, the adhesive copolymer comprises 51 to 99 parts by weight Guerbet (meth) acrylate, based on 100 parts total monomer.

Preferably, the Guerbet alkanol is derived from a straight chain alkanol, ie, R ¹ and R ² are straight chain alkyl groups. Surprisingly, it has been found that such (linear) Guerbet alkanol (meth) acrylate esters provide lower T _g and storage modulus compared to monomers in which R ¹ and R ² are branched. ing. The T _g of the resulting adhesive (co) polymer is −20 ° C. or lower, preferably −30 ° C. or lower, and most preferably −40 ° C. or lower.

The T _g value (glass transition temperature) of any polymer composition and / or layer described throughout this description is typically measured, for example, by differential scanning calorimetry (DSC) or thermomechanical analysis (TMA). Can be done.

The pressure sensitive adhesive copolymer for use in the multilayer PSA film of the present invention may further comprise internally polymerized monomer units of C _{1 to} C ₁₂ (meth) acrylate ester monomers. Examples of suitable monomers for use as C ₁ ~ ₁₂ (meth) acrylate ester monomer, non-tertiary alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pen Tanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 3-methyl-1 -Pentanol, 2-ethyl-1-butanol, 3,5,5-trimethyl-1-hexanol, 3-heptanol, 1-octanol, 2-octanol, isooctyl alcohol, 2-ethyl-1-hexanol, 1- Decanol, 2-propylheptanol, 1-dodecanol, 1-tridecanol, 1- Examples include esters of tetradecanol, citronellol, dihydrocitronellol, and the like, and either acrylic acid or methacrylic acid. In some embodiments, a combination of two or more different (meth) acrylate ester monomers is preferred, but preferred (meth) acrylate ester monomers are butyl alcohol or isooctyl alcohol, or combinations thereof and (meth) An ester with acrylic acid.

  Acrylic PSA is typically derived from petroleum-based raw materials. Increased prices for oil and associated petroleum derivatives have led to price increases for many adhesive products and destabilization of supply. Therefore, it is highly desirable to replace all or part of petroleum-based raw materials with those derived from renewable resources such as plants, but it is relatively inexpensive and thus economically and socially Because it is beneficial. Therefore, the need for such plant-derived materials is increasing.

  In a preferred embodiment, the present invention provides a composition of opposing layers of the multilayer PSA film of the present invention derived from renewable resources. Specifically, the present invention provides opposing layer compositions that are at least partially derived from plant material.

  Thus, in a preferred embodiment, the present invention provides opposing layer compositions for multilayer PSA films derived from renewable resources. Specifically, the present invention provides opposing layer compositions that are at least partially derived from plant material. This includes embodiments where not only one of the layers, but some or all of the layers of the multilayer PSA film are derived from renewable resources. Many (meth) acrylate monomers used herein can be derived from renewable resources. In some embodiments, preferred (meth) acrylate ester monomers are derived from (meth) acrylic acid and renewable resources, such as alkanols such as 2-octanol, citronellol, dihydrocitronellol, and renewable An ester with a Guerbet alkanol derived from the material. It is particularly preferred that the 2-alkyl alkanol (meth) acrylate ester, specifically Guerbet alkanol ester, and / or 2-octyl (meth) acrylate is completely derived from the biological material.

  In such a more preferred embodiment, the multilayer PSA film according to the present invention is such that the polymerizable precursor of the polymer base material to form the corresponding layer comprises 2-octyl (meth) acrylate, and the polymerizable precursor is ( Preferably 85 to 99.5% by weight of 2-octyl (meth) acrylate, more preferably 90 to 99.5% by weight (based on the total weight of the polymerizable mixture used to form the corresponding layer). It is characterized by including. According to an even more preferred embodiment of the multilayer PSA film of the present invention, the polymerizable precursor of the polymer base material for forming the opposing layers comprises 2-octyl (meth) acrylate, the polymerizable precursor is: Preferably 85 to 99.5 wt%, more preferably 90 to 99.5 wt% 2-octyl (meth) acrylate (based on the total weight of the polymerizable mixture used to form the opposing layers) including.

  Acrylic compositions containing 2-octyl (meth) acrylate are described in detail in US Pat. No. 7,385,020 B2, the contents of which are hereby incorporated by reference.

  The preferred composition of the opposing layers is derived from 2-octyl (meth) acrylate and has comparable properties when compared to other isomers of octyl (meth) acrylate such as n-octyl and isooctyl. I will provide a. Furthermore, the composition of the opposing layer has a lower viscosity than adhesives derived from other octyl isomers such as isooctyl acrylate. A low viscosity composition is more convenient and easier to coat.

  2-Octyl (meth) acrylates may be prepared by conventional techniques from 2-octanol and (meth) acryloyl derivatives such as esters, acids, and acyl halides. 2-Octanol can be prepared by treating ricinoleic acid derived from castor oil (or its ester or acyl halide) with sodium hydroxide followed by distillation from the co-product sebacic acid.

  However, the use of chain transfer agents is generally not necessary. Applicants have found that when an instant 2-octyl (meth) acrylate composition is compared to an isomeric octyl (meth) acrylate, usually at the same concentration and under the same polymerization conditions, the viscosity of its own and its solution is I found it smaller. Without being bound by theory, it is believed that instant octyl (meth) acrylate, which has a tertiary hydrogen atom at the α-position of the ester hydroxyl oxygen atom, functions as an “internal” chain transfer agent to control molecular weight. It has been.

  More preferably, the opposing layers are at least partly derived from biological material, in particular from plant material, while in particular at least 25% by weight, preferably at least 40% by weight of the monomers are derived from biological material. . This is advantageous to provide a multilayer PSA film that is at least partly made of “green” resources, is more usable without destroying the environment, and reduces the dependence on mineral oil and its price increases. . In the term “derived from biological material” it means that from a particular chemical component, at least part of its chemical structure, in particular at least 50% by weight of its structure, consists of biological material. This definition is in principle the same as for biodiesel fuel, where only the fatty acid part usually consists of biological resources, while methanol may likewise consist of fossil raw materials such as coal or mineral oil.

In some embodiments, it is desirable that the C ₁ -C ₁₂ (meth) acrylate ester monomer comprises a high T _g monomer having a T _{g of} at least 25 ° C., preferably at least 50 ° C. Examples of suitable monomers useful in the present invention include, but are not limited to, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl. Examples include methacrylate, stearyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, 3,3,5 trimethylcyclohexyl acrylate, cyclohexyl acrylate, N-octyl acrylamide, and propyl methacrylate or combinations.

  It is highly preferred that the (co) polymer comprises isobornyl acrylate, isobornyl methacrylate, and / or N-vinylcaprolactam. The amount of these comonomers is preferably selected within the range of 10 to 50 parts by weight, in particular 15 to 40 parts by weight. These comonomers exhibit particularly good release performance and shear resistance on LSE substrates, even without the use of tackifiers or even with relatively low amounts of tackifiers.

When present, the C _{1 to} C ₁₂ (meth) acrylate ester monomer is present in an amount of 1 to 49 parts by weight based on 100 parts of total monomer. Most _preferably, C 1 _{-C 12} (meth) acrylate ester monomer, 100 parts of total monomer present in an amount of 5 to 45 parts by weight based. When high _Tg monomers are included, the copolymer may include up to 50 parts by weight, preferably 10-20 parts by weight, of 100 parts by weight of the C ₁ -C ₁₂ (meth) acrylate ester monomer component.

  The pressure sensitive adhesive copolymer may further comprise an acid functional monomer, wherein the acid functional group may be essentially an acid, such as a carboxylic acid, or a portion thereof, such as a salt thereof, such as an alkali metal carboxylic acid. It may be a salt. Useful acid functional monomers include, but are not limited to, those selected from ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof. Examples of such compounds include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, β-carboxyethyl (meth) acrylate, 2-sulfoethyl methacrylate, styrene sulfone. Those selected from acids, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, and mixtures thereof.

  Due to availability, the acid functional monomers of the acid functional copolymer are generally selected from ethylenically unsaturated carboxylic acids, ie (meth) acrylic acids. If even stronger acids are desired, acidic monomers include ethylenically unsaturated sulfonic acids and ethylenically unsaturated phosphonic acids. The acid functional monomer is generally used in an amount of 0-15 parts by weight, preferably 0.5-15 parts by weight, most preferably 0.5-5 parts by weight, based on 100 parts by weight of total monomers.

  The pressure sensitive adhesive copolymer may further comprise a polar monomer. The polar monomers useful for the preparation of the copolymer have some degree of both oil-soluble and water-soluble properties, resulting in partitioning of the polar monomer between the water phase and the oil phase during emulsion polymerization. As used herein, the term “polar monomer” does not include acid functional monomers and ketone monomers. Particularly useful are monomers having acidic groups and single ethylenically unsaturated groups (ie acidic monomers). These monomers are typically polar or strongly polar. Polarity (ie hydrogen bonding capacity) is often described using terms such as “strong”, “moderately” and “weak”. References describing these and other solubility terms include “Solvants”, Paint Testing Manual, 3rd ed. , G. G. Seward, Ed. , American Society for Testing and Materials, Philadelphia, Pennsylvania, and “A Three-Dimensional Approach to Solidity”, Journal of Tol. 38, no. 496, pp. 269-280. Some examples of polarity discrimination will be described. Specifically, useful representative examples of strongly polar monomers are acrylic acid, methacrylic acid, itaconic acid, hydroxyalkyl acrylate, acrylamide, and substituted acrylamide, while N-vinyl pyrrolidone, N-vinyl caprolactam, for example. Acrylonitrile, vinyl chloride, diallyl phthalate, and N, N-dialkylamino (meth) acrylate are typical examples of moderately polar monomers. Further examples of polar monomers include cyanoacrylate, fumaric acid, crotonic acid, citronic acid, maleic acid, β-carboxyethyl acrylate, or sulfoethyl methacrylate. The alkyl (meth) acrylate monomers listed above are typical examples of relatively weakly polar monomers. These examples are given for illustrative purposes only and are not to be understood as limiting.

  The highly polar monomer may be present in an amount of 0-10 parts by weight, preferably 0.5-10 parts by weight, based on 100 parts by weight of total monomers.

  The pressure sensitive adhesive copolymer of the multilayer PSA film according to the present invention may further comprise other vinyl monomers. When used, vinyl monomers useful in (meth) acrylate polymers include vinyl esters (eg, vinyl acetate and vinyl propionate), styrene, substituted styrenes (eg, α-methylstyrene), vinyl halides, and these A mixture is mentioned. As used herein, vinyl monomers do not include acid functional monomers, acrylate ester monomers, and polar monomers. Such vinyl monomers are generally used in 0-5 parts by weight, preferably 1-5 parts by weight, based on 100 parts by weight of total monomers.

  There are two main cross-linking mechanisms in acrylic adhesives. That is, free radical copolymerization of polyfunctional ethylenically unsaturated groups with other monomers, and covalent bonding or ionic crosslinking with functional monomers such as acrylic acid. Another method is to use UV crosslinkers such as copolymerizable benzophenones or post-added photocrosslinkers such as multifunctional benzophenones and triazines. In the past, a variety of different materials have been used as crosslinkers, such as multifunctional acrylates, acetophenone, benzophenone and triazine. Crosslinking can also be achieved using high energy electromagnetic radiation such as gamma or electron beam radiation. In this case, an additional cross-linking agent may not be required.

  In other methods of crosslinking, thermal crosslinking agents may be used in combination with suitable accelerators and retarders if desired. Thermal crosslinkers suitable for use herein include isocyanates, more specifically sterically hindered isocyanates without trimerized isocyanates and / or blocking agents, or other epoxides such as epoxide-amine crosslinker systems. Compounds, but are not limited to these. Advantageous crosslinker systems and methods are described, for example, in German Patent No. 202009013255 U1, European Patent Nos. 2 305 389 A, No. 2 414 143 A, No. 2 192 148 A, No. 2 186 869, No. 0 752 435 A, No. 1 802 722 A, No. 1 791 921 A, No. 1 791 922 A, No. 1 978 069 A, and German Patent No. 10 2008 059 050 A. And related contents are incorporated herein by reference. Suitable accelerator and retarder systems for use herein are described, for example, in the description of US 2011/0281964 A1, the relevant contents of which are hereby incorporated by reference. Particularly suitable thermal crosslinkers for use herein include epoxycyclohexyl derivatives, particularly Cytec Industries Inc. And epoxy cyclohexyl carboxylate derivatives having a particular preference for (3,4-epoxycyclohexane) methyl 3,4-epoxycyclohexyl carboxylate, which is commercially available under the trade name UVACURE 1500.

  In order to increase the adhesive strength of the coated adhesive composition, a multifunctional (meth) acrylate may be incorporated into the blend of polymerizable monomers. Polyfunctional acrylates are particularly useful for emulsion or syrup polymerization. Examples of useful multifunctional (meth) acrylates include di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate, such as 1,6-hexanediol di (meth) acrylate, poly (ethylene) Glycol) di (meth) acrylate, polybutadiene di (meth) acrylate, polyurethane di (meth) acrylate, and propoxylated glycerin tri (meth) acrylate, and mixtures thereof, but are not limited thereto. The amount and identity of the multifunctional (meth) acrylate is adjusted depending on the application of the adhesive composition. Typically, the multifunctional (meth) acrylate is present in an amount of less than 5 parts based on the total dry weight of the adhesive composition. More specifically, the crosslinking agent may be present in an amount of 0.01 to 5 parts, preferably 0.05 to 1 part, based on 100 parts of the total monomer of the adhesive composition.

In some embodiments, the copolymer of the PSA film of the present invention is based on 100 parts by weight total monomer.
a) a (meth) acrylic acid ester monomer of 2-alkylalkanol having a molar carbon number average of 12 to 32, up to 100, preferably 51 to 99, more preferably 55 to 95 parts by weight;
b) 0 to 49, preferably _{1 to} 45, more preferably 5 to 45 parts by weight of a (meth) acrylic acid ester of a C _{1 to} C ₁₂ alkanol,
c) 0-15, preferably 0.1-10, most preferably 0.5-5 parts by weight of acid-functional ethylenically unsaturated monomer,
d) 0-10, preferably 0.5-10 parts by weight of a non-acid functional ethylenically unsaturated polar monomer,
e) 0-5, preferably 1-5 parts by weight vinyl monomer, and f) 0-5, preferably 0.01-5, most preferably 0.05-1 part polyfunctional (meth) acrylate. But you can.

  The adhesive (co) polymers herein may be prepared by any conventional free radical polymerization method, including dissolution, radiation, bulk, dispersion, emulsification, and suspension processes. For optical applications, dissolution, UV and bulk processes are preferred. Other processes may introduce birefringent materials or foreign objects that can affect the optical properties. The resulting adhesive (co) polymer can be a random or block (co) polymer.

  Adhesive copolymers are described in U.S. Pat. Nos. 3,691,140 (Silver), 4,166,152 (Baker et al.), 4,636,432 (Shibano et al.), 4,656, It may be prepared via suspension polymerization as disclosed in 218 (Kinoshita) and 5,045,569 (Delgado).

  The water-soluble and oil-soluble initiators useful in the preparation of the (meth) acrylate adhesive copolymers used in the present invention are initiators that, when exposed to heat, generate free radicals that initiate (co) polymerization of the monomer mixture. It is an agent. A water-soluble initiator is preferred for preparing a (meth) acrylate polymer by emulsion polymerization. Suitable water soluble initiators include, but are not limited to, potassium persulfate, ammonium persulfate, sodium persulfate, and mixtures thereof; the group consisting of the above persulfates and sodium metabisulfite and sodium bisulfite. A redox initiator such as a reaction product with a reducing agent such as selected from: and 4,4′-azobis (4-cyanopentanoic acid) and its soluble salts (eg, sodium, potassium) Those selected from the group can be mentioned. A preferred water-soluble initiator is potassium persulfate. Suitable oil-soluble initiators include, but are not limited to, E.I. I. du Pont de Nemours Co. Such as VAZO ™ 64 (2,2'-azobis (isobutyronitrile)) and VAZO ™ 52 (2,2'-azobis (2,4-dimethylpentanenitrile)) available from Those selected from the group consisting of azo compounds, peroxides such as benzoyl peroxide and lauroyl peroxide, and mixtures thereof. A preferred oil-soluble thermal initiator is (2,2'-azobis (isobutyronitrile)). When used, the initiator is about 0.05 to about 1 part by weight, preferably about 0.1 to about 0.5 part by weight, based on 100 parts by weight of the monomer component, and is a pressure sensitive adhesive. May be included.

  Polymerization by emulsification techniques may require the presence of an emulsifier (sometimes called an emulsifying agent or surfactant). Emulsifiers useful in the present invention include those selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and mixtures thereof.

  Preferably, the emulsion polymerization is carried out in the presence of an anionic surfactant (s). A useful range of surfactant concentration is from about 0.5 to about 8 weight percent, preferably from about 1 to about 5 weight percent, based on the total weight of all monomers of the emulsion pressure sensitive adhesive.

  Alternatively, the copolymer can be polymerized by techniques that include, but are not limited to, conventional techniques of solvent polymerization, dispersion polymerization, and solventless bulk polymerization. The monomer mixture may contain a type and amount of polymerization initiator, particularly a thermal initiator or photoinitiator, as described above, effective to polymerize the comonomer.

  The copolymerizable mixture may further include a chain transfer agent to control the molecular weight of the resulting polymer, if desired. Examples of useful chain transfer agents include, but are not limited to, those selected from the group consisting of carbon tetrabromide, alcohols, mercaptans, and mixtures thereof. When present, preferred chain transfer agents are isooctyl thioglycolate and carbon tetrabromide. The polymerizable mixture, if used, is up to about 0.5 parts by weight, typically from about 0.01 parts to about 0.5 parts by weight, preferably based on 100 parts by weight of the total monomer mixture. About 0.05 parts by weight to about 0.2 parts by weight of a chain transfer agent may be further included.

  A typical solution polymerization process involves adding monomers, a suitable solvent, and optionally a chain transfer agent to the reaction vessel; adding a free radical initiator; purging with nitrogen; Depending on the size and temperature, it is carried out by maintaining the elevated temperature, typically in the range of about 40-100 ° C., typically for about 1-20 hours until the reaction is complete. Examples of solvents are methanol, tetrahydrofuran, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and ethylene glycol alkyl ether. These solvents can be used alone or as a mixture thereof.

  In a typical photopolymerization method, the monomer mixture may be irradiated with ultraviolet (UV) radiation in the presence of a photopolymerization initiator (ie, photoinitiator). A preferred photoinitiator is Ciba Specialty Chemical Corp. , Tarrytown, NY under the trade names IRGACURE ™ and DAROCUR ™, 1-hydroxycyclohexyl phenyl ketone (IRGACURE ™ 184), 2,2-dimethoxy-1,2-diphenylethane -1-one (IRGACURE 651), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE ™ 819), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one (IRGACURE ™ 2959), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (IRGACURE ™ 369), 2-methyl-1- [4- (Methylthio) phenyl]- - morpholino-1-one (IRGACURE (TM) 907), and 2-hydroxy-2-methyl-(DAROCUR (TM) 1173) and the like. Particularly preferred photoinitiators are IRGACURE ™ 819, 651, 184, and 2959.

  Solvent-free polymerization methods such as the continuous free radical polymerization method described in US Pat. Nos. 4,619,979 and 4,843,134 (Kotnour et al.); US Pat. No. 5,637,646 ( A packaged pre-adhesive composition as described in US Pat. No. 5,804,610 (Hamer et al.); And an essentially adiabatic polymerization process using a batch reactor described in Ellis). Polymers can also be prepared using the methods described for polymerizing.

  The pressure sensitive adhesive composition for use in the multilayer PSA film according to the present invention may also contain one or more conventional additives. Preferred additives include tackifiers, plasticizers, dyes, antioxidants, and UV stabilizers. Such additives can be used if they do not affect the superior properties of the emulsion pressure sensitive adhesive.

  Conventional acrylic adhesives do not adhere well to certain substrates such as certain types of automotive paints and low surface energy olefin surfaces. Efforts to improve the adhesion of acrylic adhesives have been developed, i.e., more strongly adhere to these types of surfaces. Tackifying is generally performed with a basic acrylic polymer. Various types of tackifiers include phenol-modified terpenes, hydrocarbon resins such as polyvinylcyclohexane and poly (t-butylstyrene), and rosin esters such as glycerol esters of rosin and pentaerythritol esters of rosin.

  Various types of tackifiers are commercially available in phenol-modified terpenes, as well as under the trade names Neuroz ™, Nutac ™ (Newport Industries), Permalyn ™, Staybelite ™, Foral ™ (Eastman). Rosin esters such as glycerol esters of rosin and pentaerythritol esters of rosin. Hydrocarbon resin tackifiers typically obtained from C5 and C9 monomers with naphtha degradation products, as well as the trade names Piccotac ™, Eastotac ™, Regalrez ™, Regalite ™ (Eastman), Arkon (Trademark) (Arakawa), Norsolene (trademark), Wintack (trademark) (Cray Valley), Nevack, LX (Nevere Chemical Co.), Hikotack (trademark), Hikorez (trademark) (Kolon Chemical trademark) Rutgers NV), Quintone (TM) (Zeon), Escorez (TM) (Exoxide Mobile Chemical), Nures (TM), and H Products available in Rez (TM) (Newport Industries) can also be used.

  Most conventional pressure-sensitive acrylic adhesives have high solubility parameters, and there are certain potential interactions between these adhesives and many tackifiers, so that stickers are available to formulators. The choice of imparting agent is limited. As a class, hydrocarbon tackifiers, and particularly hydrogenated hydrocarbon resins, are typically not suitable for use in polar acrylic adhesive formulations due to their non-polar nature.

  The rosin acid tackifier and selected phenol-modified terpenes and α-pinene resins work well with various conventional acrylic pressure sensitive adhesives. However, there are still some problems that limit the range of tackifiers used in such acrylic adhesives. Tackified acrylic pressure sensitive adhesive formulations are often discolored or yellow. The yellow appearance of these tackified acrylic pressure-sensitive adhesives is directly attributable to the fact that many of these tackifiers are originally yellowish. Even in the case of lighter colored resins, this fading may even progress further with time and exposure to light. Acrylic adhesives that do not contain a tackifier typically have excellent aging characteristics.

  A tackified conventional acrylic pressure sensitive adhesive may be cloudy in appearance, indicating that the transparent properties found in many of the conventional acrylate pressure sensitive adhesive compositions are impaired. This turbidity is an indicator that the tackifier and acrylic polymer have limited compatibility or are incomplete. As is clear from the fact that the tackiness is impaired or the peel adhesion strength is reduced, the compatibility may be limited, and the adhesive properties may deteriorate with time. In some cases, when a tackifier is added to an adhesive composition having an acrylic monomer, polymer, oligomer, and any mixture thereof, it may be transparent and clearly compatible. . However, after removal of the solvent, after curing of the adhesive, or after time, the adhesive begins to become turbid and may exhibit some degree of insolubility between the tackifier and the acrylic polymer.

  In addition to the decrease in transparency and stability of acrylic adhesives with added adhesive, other adverse effects may be observed when a tackifier is present during the bulk acrylic polymerization reaction. is there. When the tackifier functions as a chain transfer agent or chain terminator, the adverse effects of the addition of the tackifier include inhibition or delay of the polymerization reaction due to the configuration of the tackifier, and / or change of the final polymer configuration Etc. Such action may adversely affect the performance and stability of acrylates polymerized in the presence of these tackifiers. Chain terminators can also produce undesirably high concentrations of volatile residues.

In many embodiments, the present disclosure provides tackified PSA compositions for use in multilayer PSA films according to the present invention that overcome the problems described in the art. Preferably, the tackifier is selected from materials that are essentially free of any ethylenic or acetylenic unsaturated bonds. Tackifiers include but are not limited to hydrogenated rosin resins, hydrogenated and esterified rosin resins, hydrogenated terpene resins, aliphatic petroleum resins, aromatic petroleum resins, aromatic petroleum resins. Examples thereof include alicyclic petroleum-based resins obtained by addition, and the like. The tackifier used is not limited to these, but hydrogenation such as Regalrez (TM) tackifier (Eastman) or Arkon (TM) (Arakawa Chemical Industries) tackifier it is preferably selected from been C ₉ petroleum resin. Such “hydrophobic tackifiers” may be used in amounts of up to 50 parts, up to 45 parts, up to 40 parts, up to 35 parts, or up to 30 parts. The amount of tackifier is, for example, in the range of 3 to 50 parts, in the range of 3.5 to 45 parts, in the range of 4 to 40 parts, with respect to 100 parts of the (meth) acrylate ester (co) polymer, It can be in the range of 4.5 to 35 parts, or in the range of 5 to 30 parts.

  As far as the stacking of multilayer PSA films according to the present invention is considered, the multilayer PSA film comprises at least a first pressure sensitive adhesive layer and an opposing layer. The opposing layer can be a non-tacky backing layer or may have pressure sensitive adhesive properties as well. In the latter embodiment, the opposing layer is a second pressure sensitive adhesive layer.

  The present invention, however, is not limited to two-layer films. For example, a multilayer PSA film according to the present invention may also have 3, 4, 5, or even more superimposed layers. In such an embodiment, it is further preferred that the outermost layer be first and second pressure sensitive adhesive layers. The layers sandwiched between are referred to as intermediate layer (s). In other words, in such an embodiment, the multilayer film includes at least one intermediate layer between the first pressure sensitive adhesive layer and the second pressure sensitive adhesive layer.

  The composition of the second pressure sensitive adhesive layer can be selected from any known PSA system. Specifically, the opposing layer and / or intermediate layer comprises a polymer selected from the group consisting of polyacrylate, polyurethane, polyolefin, polystyrene, natural rubber, synthetic rubber, polyvinylpyrrolidone, and any combination or mixture thereof. Including.

  However, the opposing layer and / or intermediate layer (s) can also be selected from pressure sensitive adhesive compositions as described in the present invention for the first PSA layer. The formulation of the second pressure sensitive adhesive layer may be the same or different compared to the first pressure sensitive adhesive layer.

  In addition to these materials listed above, the opposing layers and / or intermediate layers may comprise or consist of a backing film. Suitable backing films include plastics (eg, polypropylene including biaxially oriented polypropylene, vinyl, polyethylene, eg, polyesters such as polyethylene terephthalate), nonwovens (eg, paper, fabrics, nonwoven scrims), metal foils , Foams (eg, polyacrylic acid, polyethylene, polyurethane, neoprene), and the like. The foam is 3M Co. , Voltek, Sekisui, and various other sources. The foam may be formed as a coextruded sheet having a pressure sensitive adhesive composition on one or both sides of the foam, or the pressure sensitive adhesive composition may be laminated to it. When the adhesive is laminated to the substrate, it may be desirable to treat the surface of the substrate to improve adhesion. Such treatment is typically selected based on the nature of the adhesive and substrate material, and includes primer treatment and surface modification (eg, corona treatment, surface wear).

  For single-sided multilayer PSA films, the face of the facing layer surface that faces the first pressure sensitive adhesive layer is typically coated with a suitable release material. Release materials are known and include, for example, materials such as silicone, polyethylene, polycarbamate, polyacryl, and the like.

  In another embodiment of the multilayer PSA film of the present invention, the first pressure sensitive adhesive layer, the opposing layer, and / or the intermediate layer is optionally filled with filler particles, microspheres, disposable microspheres. Disposable microspheres or gas cavities, preferably filled with pentane, glass beads, glass microspheres, hydrophobic silica type fillers, hydrophilic silica type fillers, fibers, conductive and And / or may comprise at least one (further) filler material, preferably selected from the group consisting of thermally conductive particles, nanoparticles, and any combination thereof, and the intermediate layer is preferably Aluminum silicate, more preferably a foamed perlite. Such fillers may be used to increase the mechanical stability of the PSA film and can also increase shear and peel force resistance.

  From the above filler particles, foamed perlite is particularly preferred. Perlite is a naturally occurring hydrated volcanic glass formed by obsidian changes. Typically, perlite is composed of silicon dioxide (70-75% by weight), aluminum oxide (12-17% by weight), sodium oxide (3-4% by weight), potassium oxide (3-5% by weight), iron oxide. (0.5 to 2% by weight), magnesium oxide (0.2 to 0.7% by weight), and calcium oxide (0.5 to 1.5% by weight). Natural perlite further contains about 3-5% water by weight.

  Perlite for use in the present invention is foamed to obtain a very low density foam within the material, which is achieved by the presence of water in the coarse perlite rock. When heating is accelerated above 870 ° C., the coarse pearlite rocks bounce as glass ore particles softened in the flame in the same manner as popcorn, and the water in the ore becomes steam and expends. Many low density bubbles are formed. This process for foaming perlite is known.

  In the present invention, the expanded pearlite is used in a particulate form, and the expanded pearlite particles specifically have an average diameter of 1 to 300 μm, specifically 10 to 150 μm. Expanded perlite particles of this size are commercially available and can be produced by crushing expanded perlite obtained by heat treatment of perlite rock as described above.

  The amount of foamed perlite that may be added to any of the layers of the multilayer pressure sensitive adhesive film of the present invention may vary over a wide range. It is particularly preferred to add foamed perlite to the opposing layers and / or intermediate layers, especially when these layers do not have PSA properties. Specifically, the foamed pearlite content may range from 1 to 30% by weight, specifically from 2 to 20% by weight, based on the composition of the backing layer. However, the present invention is not limited to the aforementioned range. Multilayer PSA films having such a content in the backing layer exhibit a particularly high peel adhesion, especially on the clearcoat surface.

  As described above, foamed pearlite is a porous material. Porosity ensures that the addition of such filler material does not increase the total weight of the PSA film, but may even reduce the total weight. Therefore, it is preferable that the foamed perlite used has a rolling compaction density of 680 to 850 mL / 100 g.

  In this context, expanded perlite particles for use herein are preferred from hydrophobic surface modification such as silane surface modification and / or hydrophilic modification such as epoxidation, amination, or acrylate functionalization. More preferably, the selected surface modification is selected. While not wishing to be bound by theory, the hydrophobic modification, for example, further strengthens the adhesion to the glass surface and results in a weaker interaction between the polymer matrix and the filler and thus the adhesion It is considered that the deformability of the agent may be improved. While still not wishing to be bound by theory, this action is thought to lead to better stress distribution within the adhesive layer, and in particular, to provide decisive and improved peel performance on the adhesive surface. . The hydrophilic modification may function to improve the adhesion of the layer in which the filler is incorporated to the polymer matrix. Epoxidation, amination, and acrylate functionalization can be accomplished, for example, by reaction with amino silanes, epoxy silanes, and acrylic silanes.

  Other additives may be included in the first pressure sensitive adhesive layer, the opposing layer, and / or the intermediate layer to change their respective properties. Such additives include pigments, tackifiers, toughening agents, toughening agents, flame retardants, antioxidants, and stabilizers. The additive is added in an amount sufficient to obtain the desired final properties.

  According to another preferred embodiment of the present invention, a multilayer PSA film is provided having a release liner on at least one of its major surfaces. Any suitable material known to those skilled in the art can be used as the release liner, such as siliconized paper or siliconized polymer film material, specifically siliconized PET film.

  The thickness of the pressure sensitive adhesive layer (s), the opposing layer, and the intermediate layer may vary over a wide range. For example, the thickness can be selected independently for each layer from 25 μm to 3,000 μm, more preferably from 75 μm to 2,000 μm, particularly preferably from 75 μm to 1,500 μm. However, it is preferred that the pressure sensitive adhesive layer (s) exhibit a lower thickness compared to the intermediate layer and / or the opposing layer. As an example, the thickness of the PSA layer may be in the range of 20-200 μm, while the opposing layers occupy 800-2000 μm in thickness. Such multilayer PSA films exhibit high peel adhesion, which is probably caused by the stabilizing action of the opposing layers that are relatively thick compared to the PSA layer.

  The present invention further relates to a method for producing a multilayer pressure sensitive adhesive film according to the present invention, wherein the first pressure sensitive adhesive layer and the opposing layer are superposed on each other.

  According to one preferred embodiment of the method, the first pressure sensitive adhesive layer and the opposing layer, and optionally the intermediate layer or layers, are prepared separately and then laminated to each other. .

  In an alternative method for producing a multilayer pressure sensitive adhesive film according to the present invention, the liquid precursor of the first pressure sensitive adhesive layer, and the opposing layer and optionally the intermediate layer (s) The liquid precursors are superimposed and then preferably cured using actinic radiation such as UV radiation, gamma (gamma) radiation, or electron beam radiation, or by thermal curing. The method is described in detail in WO2011094385 (A1), the contents of which are incorporated herein by reference.

  However, the production of the multilayer film of the present invention is not limited to the method described above. For example, multilayer PSA films may be produced by coextrusion, solvent based methods, or combinations thereof as well.

  The present invention further provides a multilayer pressure sensitive adhesive as a PSA film for bonding the first pressure sensitive adhesive layer of the multilayer pressure sensitive adhesive film according to the present invention to an LSE substrate surface, preferably a clear coat surface. Relates to the use of film.

As noted above, the multilayer PSA film according to the present invention is particularly useful for forming strong adhesive bonds to low surface energy (LSE) substrates. As used herein, a low surface energy substrate is less than about 45 × 10 ⁵ N / cm (45 dyne per centimeter), more typically about 40 × 10 ⁵ N / cm (per centimeter). Having a surface energy of less than 40 dyne), and most typically less than about 35 × 10 ⁵ N / cm (35 dyne per centimeter). Such materials include polypropylene, polyethylene (eg, high density polyethylene or HDPE), polystyrene, poly (methyl methacrylate) (PMMA), and many clearcoat surfaces, particularly those used in the automotive industry. Other substrates may also have low surface energy characteristics due to residues such as petroleum residues or coatings such as paints present on the surface of the substrate. Existing adhesives also adhere well to substrates with low surface energy, but the adhesives of the present invention not only adhere to substrates with low surface energy, but also have high surface energy such as other resins, ceramics It has been found that it can adhere well to substrates such as glass (eg glass) and metals.

Item 1 is a multi-layer pressure sensitive adhesive (PSA) film having a first pressure sensitive adhesive layer and at least one opposing layer, wherein the first pressure sensitive adhesive layer is
a) a (meth) acrylate ester of a 2-alkylalkanol, wherein the 2-alkylalkanol has a molar carbon number average of 12 to 32, and optionally,
(b) a (meth) acrylate ester of C _1-12 alkanol, wherein (a) and b) (meth) acrylate ester having an average alkanol molar carbon number of 12-32;
Wherein the at least one opposing layer comprises at least one filler material selected from the group of filler particles, wherein the filler particles are expanded perlite. , The average number of moles of 2-alkylalkanol is defined by the following formula, the total number of moles of each alkanol (2-alkylalkanol and _C1-12 alkanol) multiplied by the number of carbons of each alkanol, It is a multilayer PSA film calculated by dividing the result by the total number of moles of alkanol.

  Item 2 is the multilayer PSA film of Item 1 in which the molar carbon number average of alkanols of a) and b) (meth) acrylic acid ester is 12-20.

  Item 3 is the multilayer PSA film of item 1 or 2, wherein the pressure sensitive adhesive composition further comprises acid monomer units and / or non-acid polar monomer units.

Item 4 is a multilayer PSA film according to any one of items 1 to 3, wherein the (co) polymer comprises b) a (meth) acrylate ester of C _1-12 alkanol.

  Item 5 is a multilayer PSA film according to any one of items 1-4, wherein the 2-alkyl alkanol is derived from a linear alkanol.

  Item 6 is a 2-alkylalkanol (meth) acrylate ester represented by the following formula:

のものであり、式中、Ｒ^{Ｇｕｅｒｂｅｔ}は、Ｃ_１２〜Ｃ_３２ ２−アルキルアルカノールから誘導され、Ｒ^３はＨ又はＣＨ_３である、アイテム１〜５のいずれか１つに従う多層ＰＳＡフィルムである。

Wherein R ^Guerbet is derived from a C ₁₂ -C ₃₂ 2- ^alkylalkanol and R ³ is H or CH ₃ is a multilayer PSA film according to any one of items 1-5 .

  Item 7 is a 2-alkylalkanol (meth) acrylate ester represented by the following formula:

のものであり、式中、Ｒ^１及びＲ^２は、それぞれ独立して、Ｃ_４〜Ｃ_１４飽和及び分枝鎖又は直鎖アルキルであり、Ｒ^３はＨ又はＣＨ_３である、アイテム６に従う多層ＰＳＡフィルムである。

Wherein R ¹ and R ² are each independently C ₄ -C ₁₄ saturated and branched or straight chain alkyl and R ³ is H or CH ₃ , according to item 6 It is a multilayer PSA film.

Item 8 is that the (co) polymer is based on 100 parts by weight total monomer,
a) 51-99 parts by weight of a (meth) acrylic acid ester monomer of 2-alkylalkanol,
b) _{1 to} 49 parts by weight of a (meth) acrylic acid ester of a C _{1 to} C ₁₂ alkanol,
c) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer,
d) 0-10 parts by weight of a non-acid functional ethylenically unsaturated polar monomer,
e) A pressure sensitive adhesive according to any one of items 1 to 7, comprising 0 to 5 parts by weight vinyl monomer, and f) 0 to 5 parts by weight polyfunctional (meth) acrylate.

Item 9 is a multilayer PSA film according to item 8, wherein the (co) polymer comprises 5 to 45 parts by weight of a (meth) acrylic ester of a C _{1 to} C ₁₂ alkanol.

  Item 10 is a multilayer PSA film according to item 8 or 9, wherein the (co) polymer comprises 0.1 to 10 parts by weight of an acid functional ethylenically unsaturated monomer.

  Item 11 is a multilayer PSA film according to any one of items 8-10, wherein the (co) polymer comprises 0.5-10 parts by weight of a non-acid functional ethylenically unsaturated polar monomer.

  Item 12 is a multilayer PSA film according to any one of items 8-11, wherein the (co) polymer comprises 0.05-1 part of a polyfunctional (meth) acrylate.

  Item 13 is a (strong) polar, wherein the (co) polymer is preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, hydroxyalkyl acrylate, acrylamide, substituted acrylamide, and any combination or mixture thereof. A multilayer PSA film according to any one of items 1 to 12, comprising

  Item 14 is a multilayer PSA film according to item 13, wherein the (co) polymer comprises preferably from 0.5 to 10 parts by weight (strong) polar acrylate, based on a total monomer of up to 10 weight percent and 100 parts by weight It is.

  Item 15 is a multilayer PSA film according to any one of items 1-14, wherein the (co) polymer comprises isobornyl acrylate, isobornyl methacrylate, and / or N-vinylcaprolactam.

  In item 16, the first pressure-sensitive adhesive layer is a tackifier, preferably 3 to 50 parts, more preferably 100 parts, of 100 parts of the (meth) acrylate ester (co) polymer. A multilayer PSA film according to any one of items 1 to 15, comprising 5 to 30 parts of a tackifier relative to the (meth) acrylate ester (co) polymer.

  Item 17 is that the tackifier is a hydrogenated rosin resin, hydrogenated and esterified rosin resin, hydrogenated terpene resin, aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, and any of them A multilayer PSA film according to item 16, selected from the group consisting of combinations or mixtures of

Item 18 has a T of ≦ −20 ° C. when the pressure sensitive adhesive of the first pressure sensitive adhesive layer, the opposing layer, and / or the intermediate layer is measured by differential scanning calorimetry (DSC). _A multilayer PSA film according to any one of items 1 to 17 having _g .

  Item 19 is a multilayer PSA film according to any one of items 1-18, wherein the (co) polymer comprises a cross-linking agent.

  Item 20 is a multilayer PSA film according to any one of items 1-19, wherein the opposing layer is a second pressure sensitive adhesive layer.

  Item 21 is a multilayer PSA film according to item 20, wherein the multilayer film includes at least one intermediate layer between the first pressure sensitive adhesive layer and the second pressure sensitive adhesive layer.

  Item 22 is a polymer base material wherein the opposing layers and / or intermediate layers are selected from the group consisting of polyacrylates, polyurethanes, polyolefins, polystyrenes, natural rubbers, synthetic rubbers, polyvinylpyrrolidones, and any combination or mixture thereof. A multilayer PSA film according to any one of items 1 to 21.

  Item 23 is that the polymerizable precursor of the polymer base material to form the opposing layer and / or intermediate layer comprises 2-octyl (meth) acrylate, and the polymerizable precursor is (the opposing layer and / or Preferably 85 to 99.5 wt%, more preferably 90 to 99.5 wt% 2-octyl (meth) acrylate (based on the total weight of the polymerizable base material used to form the interlayer). A multilayer PSA film according to any one of items 1 to 22

  Item 24 includes a pressure sensitive adhesive composition and / or a polymerizable precursor of a polymer-based material to form opposing layers and / or interlayers, at least partially on biological material, preferably on plant material. Preferably at least 25%, preferably at least 40% by weight of the polymerizable precursor of the polymer-based material to form the pressure-sensitive adhesive composition and / or the opposing layers and / or interlayers A multilayer PSA film according to any one of items 1 to 23, derived from biological material.

  Item 25 is a multilayer PSA film according to any one of items 23 or 24, in which 2-octyl (meth) acrylate is completely derived from biological material.

  Item 26 is a disposable microsphere or gas cavity in which the first pressure sensitive adhesive layer and / or intermediate layer is filled with filler particles, microspheres, disposable microspheres, preferably pentane, glass beads, glass microspheres. At least one selected from the group consisting of: hydrophobic silica type fillers, hydrophilic silica type fillers, fibers, conductive and / or thermally conductive particles, nanoparticles, and any combination or mixture thereof A multilayer PSA film according to any one of items 1 to 25 comprising a filler material and the intermediate layer preferably comprising aluminum silicate, more preferably foam perlite.

  Item 27 has an opposing layer of filler particles, microspheres, disposable microspheres, preferably disposable microspheres or gas cavities filled with pentane, glass beads, glass microspheres, hydrophobic silica type fillers, hydrophilic Any of items 1-26, including additional filler materials preferably selected from the group consisting of silica-type fillers, fibers, conductive and / or thermally conductive particles, nanoparticles, and any combination or mixture thereof. Is a multilayer PSA film according to one.

  Item 28 is a multilayer PSA film according to any one of items 1-27 wherein the foamed perlite exhibits a surface modification, preferably selected from a hydrophobic surface modification and / or a hydrophilic surface modification. A preferred hydrophobic surface modification includes silane surface modification. Preferred hydrophilic surface modifications include epoxidation, amination, and / or acrylate functionalization.

  Item 29 is a multilayer PSA film according to any one of items 1-28, wherein the PSA film is provided on at least one of its major surfaces with a release liner.

  Item 30 is a method for manufacturing a multi-layer pressure sensitive adhesive film according to any one of items 1 to 29, whereby a first pressure sensitive adhesive layer and an opposing layer overlap each other. Is the method.

  Item 31 is a method according to item 30, wherein the first pressure sensitive adhesive layer and the opposing layer are prepared separately and then laminated together.

  Item 32 is a method according to item 30 wherein the liquid precursor of the first pressure sensitive adhesive layer and the liquid precursor of the opposing layer are superimposed and then cured, preferably by actinic radiation or thermal curing. is there. Preferred actinic radiation includes UV radiation, γ (gamma) radiation, and electron beam radiation.

  Item 33 is a PSA film for securing the first pressure sensitive adhesive layer of the multilayer pressure sensitive adhesive film according to any one of items 1 to 29 to the LSE substrate surface, preferably the clear coat surface. Is the use of.

  The invention is described in more detail in conjunction with the following examples.

Applicable test methods:
90 ° peel test at 300 mm / min (in accordance with test method, Finat No. 2):
A multilayer pressure sensitive adhesive film strip according to the present invention and having a width of 10 mm and a length of> 175 mm is cut from the sample material in the machine direction.

  For test sample preparation, the liner is first removed from one adhesive side and placed on an aluminum strip having the following dimensions 22 × 1.6 cm. Next, the adhesive-coated side of each multilayer PSA film strip is placed on the clean side of the test panel with light acupressure with the adhesive side down after removing the liner. Next, the test sample was rotated twice in each direction at a speed of about 10 mm per second using a standard FINAT test roller (6,8 kg weight) to provide intimate contact between the adhesive mass and the surface. Get. After the pressure sensitive adhesive film strip has been applied to the test panel, the test sample can be subjected to ambient room temperature (23 ° C. + / − 2 ° C., 50% relative humidity +/− 5%) for 20 minutes prior to testing. Or dwell for 72 hours.

  For the peel test, the test material is clamped and fixed in the lower movable gripper of a Zwick tensile tester (Model Z020, commercially available from Zwick / Roell GmbH, Ulm, Germany) as a first step. The multilayer pressure sensitive adhesive film strip is folded at an angle of 90 ° and its free end is grasped in the upper grip of the tensile tester in a configuration commonly used for 90 ° measurement. The tensile tester is set to a grip separation speed of 300 mm per minute. Test results are expressed as Newton per 10 mm (N / 10 mm). The quoted peel value is the average of two 90 ° peel measurements.

Static shear test at 70 ° C. with a 500 g hanging weight (test method, according to Finat No. 8):
Static shear is a measure of adhesive stickiness or internal strength. It is measured in units of time (minutes) required to pull the reference area of the adhesive sheet material from the stainless steel test panel under constant stress and standard load.

  A 10 mm wide and 20 mm long multilayer PSA film strip is cut from the sample in the machine direction. Next, one of the attached surface liners is removed and the sample is placed on the aluminum backing with the desired foam surface. The second release liner is then removed and the foam is attached to the test substrate (plate) using light finger pressure to provide a 20 x 10 mm anchoring area. A standard FINAT test roller (6.8 kg weight) is rotated twice in each direction at a speed of about 10 mm per second to obtain intimate contact between the adhesive mass and the substrate surface (test plate). After the foam strip (sample) is applied to the test plate, the test plate is allowed to dwell for 24 hours at room temperature (23 ° C. + / − 2 ° C., 50% relative humidity +/− 5%) prior to testing.

  Place the test panel on a shear holding device. After a stop time of 10 minutes at a temperature of 70 ° C. for Uregloss and 90 ° C. for VW-2K, a 500 g load is suspended in a hole on the test panel. Start the timer. Results are recorded in minutes until failure and are the average of two shear measurements. The recorded time of “10000+” indicates that the tape does not break after 10,000 minutes and the test is terminated there.

Test sample:
The adhesive test is performed on the following clearcoat panels for automobiles.
UreGloss clear coat coating panel commercially available from BASF Coatings.
CeramiClear 5 coated panel, commercially available from PPG Industries.
VW 2K clear coat coated panels available from BASF coatings.

  The clear coats listed above include acrylic resins and polyesters, which are either alone or copolymers containing hydroxy or glycidyl functionality or carbamic acid residues (groups), or acrylic esters. And a mixture of copolymers of methacrylic acid esters with hydroxyl groups, free acid groups, and further comonomers (eg styrene). Panels are cut to the required dimensions prior to 90 ° peel and shear testing.

  Prior to testing, the automotive clearcoat coated panels are washed with a 1: 1 mixture of isopropyl alcohol and distilled water for Uregloss and VW 2K clearcoats, or n-heptane for CeramiClear 5 clearcoats. The test panel is then wiped dry with a paper tissue.

Raw materials used:
In the examples, the following raw materials are used.
Isooctyl acrylate is an ester of isooctyl alcohol and acrylic acid and is obtained from 3M Hilden, Germany (IOA).

  2-Ethylhexyl acrylate (C8-acrylate, 2-EHA) is an ester of 2-ethylcohol and acrylic acid, Tg value obtained from BASF AG, Germany: -58 ° C.

  Prepared as disclosed in 2-octyl acrylate (2-OA), US Pat. No. 7,385,020 B2 (Preparation Example 1).

  HEDA 16 (branched C16 acrylate) is an ester from C16 guarbet alcohol and acrylic acid and is commercially available from Toho Chemical Industry, Japan.

  NK Ester ISA (branched C18 acrylate) is an ester from C18 guerbet alcohol and acrylic acid and is commercially available from Shin Nakamura Chemical, Japan.

  Acrylic acid is obtained from 3M Hilden, Germany (AA).

  Isobornyl acrylate (SR 506D) is a monofunctional acrylic monomer having a high Tg of 66 ° C. and is available from Cray Valley, France.

  N-vinylcaprolactam is a monofunctional acrylic monomer having an amide group in the side chain and is available from BASF AG, Germany.

  Regalite R-1125 is a low molecular weight, fully hydrogenated hydrocarbon resin, commercially available from Eastman Chemical BV, NL.

  Regalite R-7100 is a partially hydrogenated hydrocarbon resin and is commercially available from Eastman Chemical BV, NL.

  1,6-hexanediol diacrylate is a fast-setting diacrylate and is obtained from 3M Hilden, Germany (HDA).

  Omnirad BDK 2,2-dimethoxy-2-phenylacetophenone is a UV initiator and is available from iGm resins, Waalwijk, The Netherlands.

  Speedcure BKL 2,2-dimethoxy-2-phenylacetophenone is a UV initiator and is available from Lambson, USA.

  Eurocell 300-h (available from Europerl, Germany) is a foamed perlite, φ particle size: 75 μm, hydrophobized with silane.

  3M Glassbubbles (K15) is a hollow glass bubble with a diameter of 115 μm and is available from 3M Germany.

  Aerosil R-972 is a hydrophobic fumed silica particle and is available from Evonik, Germany.

Preparation of liquid precursor:
1. Preparation of foam liquid precursors (LPF1 and LPF2):
The liquid precursors of the foam (ie, the opposing layers) are hereinafter referred to as LPF1 and LPF2, but with 90 wt% 2-EHA (LPF1) or 2-OA (LPF2) with 0.04 pph Omnirad BDK. Prepare by combining 10 wt% acrylic acid in a glass container. Prior to initiating UV exposure, the mixture is flushed with nitrogen for 10 minutes and nitrogen is constantly bubbled into the mixture until the polymerization process is stopped by adding air to the syrup. The mixture is always stirred with a propeller stirrer (300 U / min) and when the viscosity of about 2000 mPas is reached, the reaction is stopped (T = 25 ° C., spindle 4,12 rpm as measured with a Brookfield viscometer). Add additional 0.16 ppH Omnirad BDK, 0,12 ppH HDDA crosslinker, 6 ppH glass bubble K15, and 6 pph Eurocell 300-h to the syrup and mix until they are completely dissolved / dispersed.

2. Preparation of the liquid precursor skin layer:
The liquid precursor for the skin layer (ie PSA layer) is hereinafter referred to as LPS 1 to LPS 21, but the corresponding amount of low Tg acrylate is low weight percent acrylic acid and 0.04 pph Omnirad BDK. Prepare by combining in a glass container. Prior to initiating UV exposure, the mixture is flushed with nitrogen for 10 minutes and nitrogen is constantly bubbled into the mixture until the polymerization process is stopped by adding air to the syrup. The mixture is always stirred with a propeller stirrer (300 U / min) and the reaction is stopped when a viscosity of about 11000 mPas is reached (T = 25 ° C., spindle 4,12 rpm as measured with a Brookfield viscometer). Additional 0.16 ppH Omnirad BDK, 0.12 ppH HDDA crosslinker, the corresponding amount of tackifier, and acrylic cocoonomer are added to the syrup and mixed until they are completely dissolved / dispersed.

Table 1 shows an overview of the liquid precursor used in the skin layer.

Liquid precursor coating and example preparation:
For the preparation of the examples, in-line application of two or more wet layers to the substrate is carried out, followed by curing, as specifically described in international patent application 2011094385 (A1). Curing is performed by a photochemical method using UV light.

  The multilayer construction produced by this method consists of layers that are smooth, homogeneous and have separate and regular interfaces to each other. Do not observe uncontrolled mixing at any time.

  For the preparation of the examples, a solvent-free siliconized PET release liner Hostaphan 2SLK, 75 μm thickness, commercially available from Mitsubishi is used. A liner is introduced into the in-line wet-on-wet coating so that it is on each side of the bilayer construction.

  To obtain an example, the liquid precursor of the skin layer used for the first pressure sensitive layer of the multilayer construction is coated on the bottom surface of the liquid precursor LPF1 or LPF2 with a thickness of about 70-90 μm. . Thereby, LPF1 and LPF2 represent the backing layer of the multilayer construction whose coating thickness is 1110-1130 μm. All examples are manufactured at a laboratory coating machine line speed of 0.71 m / min.

  The laboratory coating machine has a 3 m long UV curing station and each zone can be operated at a different UV intensity. Curing takes place both from the top, i.e. towards the exposed liquid precursor layer optionally coated with a release liner, and from the bottom, i.e. towards the substrate, thereby bi-directionally. The supplied intensity is set to an equal level. Irradiation is supplied by a fluorescent lamp at a wavelength of 300-400 nm, which is a maximum at 351 nm. The total irradiation intensity cumulatively irradiated from the top and bottom and the length of each of the two coating zones were as listed in Table 2.

  The UV curing of the multilayer construction embodiment is performed both from the top and from the bottom, so the UV intensity is set to an equal level in all zones.

  A coating unit filled with a liquid precursor is mounted upstream of the UV curing station. The liquid precursor is coated on top of each other on the bottom liner. The top liner is guided through the bottom web chamber of the coating unit.

Structures of Examples 1 to 21 Table 3 shows structures of Examples 1 to 21.

  Chamber I is then provided with a first liquid precursor, i.e. the containment vessel upstream from the first coating knife, while chamber II is between the first coating knife and the second coating knife. The container corresponding to the 2nd precursor arrange | positioned in this is pointed out.

Test results:
The 90 ° peel values for Examples 1 (Ex.1) to 6 (Ex.6) on three different automotive clearcoats are listed in the following three tables (Tables 4-6). The 90 ° peel adhesion value is measured after a test sample stop time of 20 minutes at 72 ° C. + / − 2 ° C. or 72 hours. Two test samples are measured for each example, the results are averaged and reported in N / 10 mm.

  The above three tables clearly show that attempts at simply lower acrylic acid content do not lead to improvements in 90 ° peel values on automotive clearcoats. Due to this, the effect of the acrylate carbon chain length does not appear to have a significant effect yet.

  In the following tables (Tables 7-9), the 90 ° peel value at the same time maintains a low level of acrylic acid at 3.5% by weight while combining the isobornyl acrylate and hydrocarbon tackifier resin. Used for three different automotive clearcoats.

  Examples 7-10 are based on HEDA acrylate (C16) with 23% by weight IBOA and increasing amounts of tackifier resin, while Examples 11-14 are based on C18 acrylate, and Example 15 -18 are based on IOA (C8) acrylate. From Table 7 above, it can be clearly seen that increasing amounts of hydrocarbon tackifier resin have little or no effect on the IOA based examples (Ex.15 to Ex.18). . In particular, a significant improvement with a tackifier loading in excess of 20% by weight is seen when using either C16 or C18 acrylate.

  The same effect as in Table 7 is seen on the CeramiClear coat. Samples containing IOA (C8) show little effect when tackified with a hydrocarbon resin and, furthermore, do not obtain high peel values at filler loadings of over 20% by weight.

  Similarly, the same effect as the above-described automobile clear coat can be seen for the VW2K clear coat. Excellent adhesion to low surface energy could be obtained by combining either C16 or C18 acrylate with a low amount of acrylic acid and by adding a third comonomer and tackifier resin.

  The previous example used isobornyl acrylate (IBOA) as the (third) comonomer. To examine the effect on 90 ° peel adhesion with an alternative (third) comonomer, Examples 19 and 20 are performed with N-vinylcaprolactam (NVC). The 90 ° peel results are shown in the attached Table 10 below.

  From Table 10, the effect of NVC can be clearly seen, especially when compared to the test results associated with the 90 ° peel values of Examples 1-6, which do not have any (third) comonomer.

  The static shear values on two different automotive clear coats UreGloss and Cerami Clear 5 are shown in Table 11 for all examples. Two samples are taken for each test substrate and the test results are averaged and reported in minutes.

  From Table 11, it can be clearly seen that the increase in acrylic acid in the skin layer was predicted by theory, but increased the shear performance of the pressure sensitive adhesive multilayer construction. In Examples 1-6, it can be further seen that the use of C18 acrylate leads to increased shear strength, especially compared to IOA. This effect, however, disappears when the formulation is added with a tackifier resin. Secondly, the shear results appear to be very comparable between IOA, C16, and C18 acrylates when IBOA is used as the (third) comonomer. However, when switching to NVC as an additional comonomer, there is a significant increase in static shear performance and the shear test results then show a 10000 minute suspension time when using the Cerami Clear 5 coated test panel as the substrate. Exceeded.

  Tables 12 and 13 are provided below, and similar peel and static shear performance can be obtained on clearcoats between examples with backing layers based on either 2-EHA or 2-OA. Show. Thereby, Table 12 shows the 90 ° peel values after 20 minutes and 72 hours of stop time on the VW 2K clearcoat, and Table 13 shows the static shear results for the same example. The selected examples are Examples 10 and 21, which both have an adhesive skin layer based on the liquid precursor LPS10 and differ only depending on the liquid precursor used to form the foam. It was either LPF 1 or LPF2.

Claims (33)

A multi-layer pressure sensitive adhesive (PSA) film having a first pressure sensitive adhesive layer and at least one opposing layer, wherein the first pressure sensitive adhesive layer comprises:
a) a (meth) acrylate ester of a 2-alkylalkanol, wherein the 2-alkylalkanol has a molar carbon number average of 12 to 32, and optionally,
b) a (meth) acrylate ester of C _1-12 alkanol, wherein the a) and b) (meth) acrylic acid ester has a molar carbon number average of 12-32 in the alkanol. When,
A pressure sensitive adhesive composition comprising a (co) polymer of
The at least one opposing layer comprises at least one filler material selected from the group of filler particles, the filler particles are expanded perlite, and the molar carbon number average of the 2-alkylalkanol is: Sum the number of moles of each alkanol (2-alkylalkanol and _C1-12 alkanol) multiplied by the number of carbons of each alkanol as defined by the following formula and _divide the result by the total number of moles of alkanol. Multilayer PSA film calculated by

  2. The multilayer PSA film according to claim 1, wherein the molar carbon number average of the alkanol of the a) and b) (meth) acrylic acid ester is 12-20.   The multilayer PSA film according to claim 1 or 2, wherein the pressure-sensitive adhesive composition further comprises an acid monomer unit and / or a non-acid polar monomer unit. The multilayer PSA film according to any one of claims 1 to 3, wherein the (co) polymer contains b) a (meth) acrylate ester of _C1-12 alkanol.   The multilayer PSA film according to claim 1, wherein the 2-alkylalkanol is derived from a linear alkanol. The 2-alkylalkanol (meth) acrylate ester has the following formula:

Are those of the ^{formula, R Guerbet} _is derived from C _{12 -C} 32 2-alkyl alkanol, characterized in that ^{R 3} is H or CH _3, any one of claims 1 to 5 A multilayer PSA film according to 1. The 2-alkylalkanol (meth) acrylate ester has the following formula:

Wherein R ¹ and R ² are each independently C ₄ -C ₁₄ saturated and branched or straight chain alkyl, and R ³ is H or CH _3. The multilayer PSA film according to claim 6. The (co) polymer is based on 100 parts by weight of total monomers,
a) 51-99 parts by weight of a (meth) acrylic acid ester monomer of 2-alkylalkanol,
b) _{1 to} 49 parts by weight of a (meth) acrylic acid ester of a C _{1 to} C ₁₂ alkanol,
c) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer,
d) 0-10 parts by weight of a non-acid functional ethylenically unsaturated polar monomer,
The multilayer according to any one of claims 1 to 7, characterized in that it comprises e) 0 to 5 parts by weight vinyl monomer, and f) 0 to 5 parts by weight polyfunctional (meth) acrylate. PSA film. The multilayer PSA film according to claim 8, wherein the (co) polymer comprises 5 to 45 parts by weight of a (meth) acrylic acid ester of a C _{1 to} C ₁₂ alkanol.   The multilayer PSA film according to claim 8 or 9, wherein the (co) polymer comprises 0.1 to 10 parts by weight of an acid functional ethylenically unsaturated monomer.   The multilayer PSA film according to any one of claims 8 to 10, wherein the (co) polymer comprises 0.5 to 10 parts by weight of a non-acid functional ethylenically unsaturated polar monomer.   The multilayer PSA film according to any one of claims 8 to 11, wherein the (co) polymer comprises 0.05 to 1 part of a polyfunctional (meth) acrylate.   The (co) polymer comprises a polar acrylate selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, hydroxyalkyl acrylate, acrylamide, substituted acrylamide, and any combination or mixture thereof, The multilayer PSA film according to any one of claims 1 to 12.   14. Multilayer according to claim 13, characterized in that the (co) polymer comprises a maximum of 10 weight percent, preferably 0.5 to 10 parts by weight of the polar acrylate, based on 100 parts by weight of total monomers. PSA film.   The multilayer PSA film according to any one of claims 1 to 14, wherein the (co) polymer comprises isobornyl acrylate, isobornyl methacrylate, and / or N-vinylcaprolactam.   The first pressure sensitive adhesive layer is a tackifier, preferably 3 to 50 parts of tackifier, more preferably 100 parts of (()) to 100 parts of the (meth) acrylate ester (co) polymer. The multilayer PSA film according to any one of claims 1 to 15, characterized in that it comprises 5 to 30 parts of tackifier relative to the (meth) acrylate ester (co) polymer.   The tackifier is a hydrogenated rosin resin, a hydrogenated and esterified rosin resin, a hydrogenated terpene resin, an aliphatic petroleum resin, an aromatic petroleum resin, an alicyclic petroleum resin, and any combination thereof or The multilayer PSA film according to claim 16, characterized in that it is selected from the group consisting of a mixture. Layer that the pressure sensitive adhesive and / or the counter of the first pressure sensitive adhesive layer, when measured by differential scanning calorimetry (DSC), to have a ≦ -20 ° C. T _g of 18. A multilayer PSA film according to any one of the preceding claims, characterized in that it is characterized in that   The multilayer PSA film according to claim 1, wherein the (co) polymer contains a crosslinking agent.   The multilayer PSA film according to any one of claims 1 to 19, wherein the facing layer is a second pressure-sensitive adhesive layer.   The multilayer PSA film of claim 20, wherein the multilayer film comprises at least one intermediate layer between the first pressure sensitive adhesive layer and the second pressure sensitive adhesive layer. .   The opposing layer and / or the intermediate layer comprises a polymer base material selected from the group consisting of polyacrylate, polyurethane, polyolefin, polystyrene, natural rubber, synthetic rubber, polyvinylpyrrolidone, and any combination or mixture thereof. The multilayer PSA film according to any one of claims 1 to 21, wherein the multilayer PSA film is characterized in that   The polymerizable precursor of the polymer base material for forming the opposing layer and / or the intermediate layer comprises 2-octyl (meth) acrylate, and the polymerizable precursor is preferably 85-99.5. 23. Multilayer PSA film according to any one of the preceding claims, characterized in that it comprises 2% by weight, more preferably 90-99.5% by weight of 2-octyl (meth) acrylate.   The pressure sensitive adhesive composition and / or the polymerizable precursor of the polymer base material to form the opposing layer and / or the intermediate layer is at least partly a biological material, preferably a plant material At least 25% by weight, preferably at least 40% by weight of the polymerizable precursor of the polymer base material to form the pressure sensitive adhesive composition and / or the opposing layer and / or the intermediate layer. 24. Multilayer PSA film according to any one of the preceding claims, characterized in that the weight percent is preferably derived from biological material.   The multilayer PSA film according to claim 23 or 24, wherein the 2-octyl (meth) acrylate is completely derived from a biological material.   The first pressure sensitive adhesive layer and / or the intermediate layer is made of filler particles, microspheres, disposable microspheres, preferably disposable microspheres or gas cavities filled with pentane, glass beads, glass microspheres, hydrophobic At least one filler material preferably selected from the group consisting of porous silica type fillers, hydrophilic silica type fillers, fibers, conductive and / or thermally conductive particles, nanoparticles, and any combination or mixture thereof The multilayer PSA film according to any one of claims 1 to 25, characterized in that said intermediate layer preferably comprises aluminum silicate, more preferably foamed perlite.   Said opposing layers are filler particles, microspheres, disposable microspheres, preferably disposable microspheres or gas cavities filled with pentane, glass beads, glass microspheres, hydrophobic silica type fillers, hydrophilic silica type fillers A further filler material, preferably selected from the group consisting of agents, fibers, conductive and / or thermally conductive particles, nanoparticles, and any combination or mixture thereof. The multilayer PSA film according to any one of 26.   28. The foamed perlite particles exhibit surface modification, more preferably selected from hydrophobic surface modification and / or hydrophilic surface modification. Multilayer PSA film.   29. A multilayer PSA film according to any one of the preceding claims, characterized in that the PSA film is provided on at least one of its major surfaces with a release liner.   30. A method for producing a multilayer pressure-sensitive adhesive film according to any one of claims 1 to 29, wherein the first pressure-sensitive adhesive layer and the opposing layer are superimposed on each other. ,Method.   31. The method of claim 30, wherein the first pressure sensitive adhesive layer and the opposing layer are prepared separately and then laminated together.   The liquid precursor of the first pressure sensitive adhesive layer and the liquid precursor of the opposing layer are superimposed and then cured, preferably by actinic radiation or heat curing. 30. The method according to 30.   30. The multi-layer pressure-sensitive adhesive for fixing the first pressure-sensitive adhesive layer of the multi-layer pressure-sensitive adhesive film according to any one of claims 1 to 29 to an LSE substrate surface, preferably a clear coat surface. Use of adhesive film as PSA film.